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WO2003086965A1 - Method and installation for separating a mixture of hydrogen and carbon monoxide - Google Patents

Method and installation for separating a mixture of hydrogen and carbon monoxide Download PDF

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Publication number
WO2003086965A1
WO2003086965A1 PCT/FR2003/001174 FR0301174W WO03086965A1 WO 2003086965 A1 WO2003086965 A1 WO 2003086965A1 FR 0301174 W FR0301174 W FR 0301174W WO 03086965 A1 WO03086965 A1 WO 03086965A1
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WO
WIPO (PCT)
Prior art keywords
unit
hydrogen
gas
decarbonation
synthesis gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/FR2003/001174
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French (fr)
Inventor
Eric Dumont
Antoine Hernandez
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA a Directoire et Conseil de Surveillance pour lEtude et lExploitation des Procedes Georges Claude
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Air Liquide SA, LAir Liquide SA a Directoire et Conseil de Surveillance pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Priority to US10/511,702 priority Critical patent/US7380413B2/en
Priority to JP2003583931A priority patent/JP4440653B2/en
Priority to EP03746341A priority patent/EP1503953B1/en
Priority to DE60313863T priority patent/DE60313863T2/en
Priority to AU2003249147A priority patent/AU2003249147A1/en
Publication of WO2003086965A1 publication Critical patent/WO2003086965A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0233—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of CnHm with 1 carbon atom or more
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/506—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0223—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0252—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0261—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of carbon monoxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0271—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of H2/CO mixtures, i.e. of synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/048—Composition of the impurity the impurity being an organic compound
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/74—Refluxing the column with at least a part of the partially condensed overhead gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00—Processes or apparatus using separation by rectification
    • F25J2200/90—Details relating to column internals, e.g. structured packing, gas or liquid distribution
    • F25J2200/94—Details relating to the withdrawal point
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/30—Processes or apparatus using other separation and/or other processing means using a washing, e.g. "scrubbing" or bubble column for purification purposes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • F25J2205/66—Regenerating the adsorption vessel, e.g. kind of reactivation gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/04—Mixing or blending of fluids with the feed stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/06—Splitting of the feed stream, e.g. for treating or cooling in different ways
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/04—Recovery of liquid products
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/30—Compression of the feed stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/02—Recycle of a stream in general, e.g. a by-pass stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/02—Internal refrigeration with liquid vaporising loop
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/24—Quasi-closed internal or closed external carbon monoxide refrigeration cycle
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S62/00—Refrigeration
    • Y10S62/931—Recovery of hydrogen

Definitions

  • This unit generally includes two bottles in continuous operation, one in production, the other in the regeneration phase.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Industrial Gases (AREA)
  • Separation Of Gases By Adsorption (AREA)

Abstract

The invention relates to a method for simultaneously producing hydrogen and carbon monoxide, whereby the synthesis gas is subjected to decarbonatation in a decarbonatation unit (2), and to desiccation in a desiccation unit (5). The remaining constituents are cryogenically separated and a hydrogen-enriched gas (7, 19, 21) is recycled upstream from the decarbonatation unit and downstream from a unit for producing synthesis gas (F).

Description

Procédé et installation de séparation d'un mélange d'hydrogène et de monoxyde de carbone Method and installation for separating a mixture of hydrogen and carbon monoxide

La présente invention est relative à un procédé et à une installation de séparation d'un mélange d'hydrogène et de monoxyde de carbone. En particulier, elle concerne un procédé de séparation d'un tel mélange utilisant une étape de séparation par distillation cryogénique.The present invention relates to a method and an installation for separating a mixture of hydrogen and carbon monoxide. In particular, it relates to a method for separating such a mixture using a separation step by cryogenic distillation.

Les unités de production de monoxyde de carbone et d'hydrogène peuvent être séparées en deux parties :The carbon monoxide and hydrogen production units can be separated into two parts:

- génération du gaz de synthèse (mélange contenant H2, CO, CH4, C02 et N2 essentiellement). Parmi les diverses voies industrielles de production de gaz de synthèse, le reformage à la vapeur d'eau est la plus importante. La conception de cette unité qui comprend un four est basée sur les productions en CO et hydrogène requises.- generation of synthesis gas (mixture containing H 2 , CO, CH 4 , C0 2 and N 2 essentially). Among the various industrial routes for the production of synthesis gas, steam reforming is the most important. The design of this unit, which includes an oven, is based on the production of CO and hydrogen required.

- purification du gaz de synthèse. On retrouve :- purification of synthesis gas. We find :

- une unité de lavage aux aminés pour éliminer la plus grande partie du C02 contenue dans le gaz de synthèse- an amine washing unit to remove most of the C0 2 contained in the synthesis gas

- une unité d'épuration sur lit d'adsorbants. Cette unité comprend généralement deux bouteilles en fonctionnement continu, une en production, l'autre en phase de régénération.- a purification unit on a bed of adsorbents. This unit generally includes two bottles in continuous operation, one in production, the other in the regeneration phase.

- une unité de traitement à basse température par un procédé cryogénique (boîte froide) pour produire du monoxyde de carbone et de l'hydrogène (dont éventuellement un mélange de monoxyde de carbone et d'hydrogène dit Oxogaz) aux débits et puretés requis par le client. Le procédé le plus fréquent est le lavage au méthane liquide qui permet d'obtenir du monoxyde de carbone pur avec un rendement de récupération pouvant atteindre 99 %, de l'hydrogène dont la teneur en CO varie généralement entre quelques ppm et 1 % et un gaz résiduaire riche en méthane utilisé comme combustible.- a low temperature treatment unit using a cryogenic process (cold box) to produce carbon monoxide and hydrogen (including possibly a mixture of carbon monoxide and hydrogen known as Oxogaz) at the flow rates and purities required by the customer. The most frequent process is washing with liquid methane which makes it possible to obtain pure carbon monoxide with a recovery yield of up to 99%, hydrogen whose CO content generally varies between a few ppm and 1% and a waste gas rich in methane used as fuel.

Des procédés de ce type sont décrits dans « Tieftemperaturtechnik » de Hausen et al., Springer-Verlag 1985 pp 417-419, EP-A-837031 , EP-A- 0359629, EP-A-0790212 et EP-A-1245533. L'équilibre thermodynamique de l'unité de génération de gaz de synthèse est favorisé par une basse pression qui se traduit par une consommation de matière première moins importante, alors que l'unité de purification de gaz de synthèse est favorisée par une haute pression en terme de taille d'équipements et de consommation électrique.Processes of this type are described in "Tieftemperaturtechnik" of Hausen et al., Springer-Verlag 1985 pp 417-419, EP-A-837031, EP-A-0359629, EP-A-0790212 and EP-A-1245533. The thermodynamic balance of the synthesis gas generation unit is favored by a low pressure which results in a lower consumption of raw material, while the synthesis gas purification unit is favored by a high pressure in term of equipment size and electrical consumption.

C'est pourquoi, et compte tenu de la limitation de la pression de fonctionnement des fours de reformage (qui opèrent à une pression inférieure à 45 bar abs.), il peut être avantageux et/ou nécessaire d'incorporer un compresseur de gaz de synthèse dans la chaîne de purification du gaz de synthèse.This is why, and taking into account the limitation of the operating pressure of reforming furnaces (which operate at a pressure below 45 bar abs.), It may be advantageous and / or necessary to incorporate a gas compressor. synthesis in the synthesis gas purification chain.

Dans la plupart des cas, l'hydrogène produit par la boîte froide, contenant jusqu'à 1 % mol. de CO, est utilisé comme gaz de régénération de l'épuration, puis est envoyé vers une unité de purification par adsorbants (PSA) avant d'être acheminé vers le client final.In most cases, the hydrogen produced by the cold box, containing up to 1% mol. of CO, is used as a gas for regeneration of the purification, then it is sent to an adsorbent purification unit (PSA) before being conveyed to the end customer.

Dans le cas où l'hydrogène produit par la boîte froide est envoyé directement vers le client avec une spécification de la teneur en CO de quelques ppm, il n'est plus possible d'utiliser ce gaz comme gaz de régénération.If the hydrogen produced by the cold box is sent directly to the customer with a specification of the CO content of a few ppm, it is no longer possible to use this gas as regeneration gas.

Dans le cas également où l'on produit un mélange de monoxyde de carbone et d'hydrogène contenant généralement 50 % d'hydrogène, la quantité d'hydrogène restante comme gaz residuaire est trop faible pour régénérer l'épuration ; il est donc nécessaire de trouver un autre gaz comme gaz de régénération.In the case also where a mixture of carbon monoxide and hydrogen generally containing 50% of hydrogen is produced, the quantity of hydrogen remaining as waste gas is too small to regenerate the purification; it is therefore necessary to find another gas as regeneration gas.

Une des solutions actuelles consiste à produire une quantité nécessaire d'hydrogène supplémentaire au niveau de l'unité de génération. Cet hydrogène contenu dans le gaz de synthèse est traité dans l'unité de purification et notamment dans l'unité de lavage au méthane, est ensuite utilisé comme gaz de régénération de l'épuration et enfin valorisé comme carburant.One of the current solutions consists in producing a necessary quantity of additional hydrogen at the level of the generation unit. This hydrogen contained in the synthesis gas is treated in the purification unit and in particular in the methane washing unit, is then used as gas for regeneration of the purification and finally valued as fuel.

Selon un objet de l'invention, il est prévu un procédé de production simultanée d'hydrogène et de monoxyde de carbone du type dans lequel on reçoit un gaz de synthèse, tel qu'un gaz de reformage d'hydrocarbures, contenant de l'hydrogène et du monoxyde de carbone provenant d'une unité de production de gaz de synthèse, on soumet le gaz de synthèse à une decarbonatation dans une unité de decarbonatation et à une dessiccation dans une unité de dessiccation, puis à une séparation cryogénique des constituants restants caractérisé en ce que l'on recycle un gaz contenant au moins 60 % d' hydrogène constitué par :According to an object of the invention, there is provided a process for the simultaneous production of hydrogen and carbon monoxide of the type in which a synthesis gas is received, such as a hydrocarbon reforming gas, containing hydrogen and carbon monoxide from a synthesis gas production unit, the synthesis gas is subjected to decarbonation in a decarbonation unit and to a desiccation in a desiccation unit, then to a cryogenic separation of the remaining constituents characterized in that a gas containing at least 60% hydrogen is recycled:

i) un gaz provenant de la séparation cryogénique et/oui) a gas from cryogenic separation and / or

ii) une partie du gaz de synthèseii) part of the synthesis gas

en amont de l'unité de decarbonatation et en aval de l'unité de production de gaz de synthèse.upstream of the decarbonation unit and downstream of the syngas production unit.

Selon d'autres aspects facultatifs de l'invention,According to other optional aspects of the invention,

- le gaz contenant au moins 60 % d'hydrogène est soutiré en tête d'une colonne de lavage au méthane de l'unité de séparation cryogénique, dans laquelle se séparent les constituants restants ;- The gas containing at least 60% hydrogen is drawn off at the head of a methane washing column of the cryogenic separation unit, in which the remaining constituents are separated;

- le gaz contenant au moins 60 % d'hydrogène est une partie du gaz le plus pur en hydrogène produit ;- the gas containing at least 60% hydrogen is a part of the purest hydrogen gas produced;

- le gaz contenant au moins 60 % d'hydrogène sert à régénérer l'unité de dessiccation avant d'être envoyé en amont de l'unité de decarbonatation ;- The gas containing at least 60% hydrogen is used to regenerate the drying unit before being sent upstream of the decarbonation unit;

- le gaz de synthèse épuré dans l'unité de decarbonatation est comprimé dans un compresseur avant d'être envoyé à l'unité de dessiccation ;- the synthesis gas purified in the decarbonation unit is compressed in a compressor before being sent to the desiccation unit;

- un autre gaz enrichi en hydrogène est envoyé de la séparation cryogénique en amont du compresseur et en aval de l'unité de decarbonatation.- another gas enriched in hydrogen is sent from the cryogenic separation upstream of the compressor and downstream of the decarbonation unit.

Selon un autre aspect de l'invention, il est prévu une installation de production simultanée d'hydrogène et de monoxyde de carbone comprenant une unité de production de gaz de synthèse, une unité de decarbonatation, une unité de dessiccation et une unité de séparation cryogénique, et des moyens reliant l'unité de production de gaz de synthèse avec l'unité de decarbonatation, l'unité de decarbonatation avec l'unité de dessiccation et l'unité de dessiccation avec l'unité de séparation cryogénique et des moyens de soutirage d'hydrogène et de monoxyde de carbone en tant que produits caractérisée en ce qu'elle comprend des moyens pour recycler un gaz contenant au moins 60 % d'hydrogène constitué par : i) un gaz enrichi en hydrogène par rapport au gaz de synthèse de l'unité de séparation cryogénique et/ouAccording to another aspect of the invention, there is provided an installation for the simultaneous production of hydrogen and carbon monoxide comprising a synthesis gas production unit, a decarbonation unit, a drying unit and a cryogenic separation unit. , and means connecting the synthesis gas production unit with the decarbonation unit, the decarbonation unit with the desiccation unit and the desiccation unit with the cryogenic separation unit and withdrawal means of hydrogen and carbon monoxide as products, characterized in that it comprises means for recycling a gas containing at least 60% of hydrogen consisting of: i) a gas enriched in hydrogen compared to the synthesis gas of the cryogenic separation unit and / or

ii) une partie du gaz de synthèseii) part of the synthesis gas

en amont de l'unité de decarbonatation et en aval de l'unité de production de gaz de synthèse.upstream of the decarbonation unit and downstream of the syngas production unit.

Les moyens pour recycler le gaz sont de' préférence reliés à la fois à un point en amont de l'unité de dessiccation et en aval de l'unité de production de gaz de synthèse et à l'unité de séparation cryogénique ou un point en amont de l'unité de séparation cryogénique.The means for recycling the gases are 'preferably connected to both a point upstream of the drying unit and downstream of the synthesis gas production unit and the cryogenic separation unit or a point in upstream of the cryogenic separation unit.

Selon d'autres aspects facultatifs de l'invention, l'installation comprend :According to other optional aspects of the invention, the installation comprises:

- des moyens de compression en aval des moyens de decarbonatation.- compression means downstream of the decarbonation means.

- des moyens pour envoyer le gaz enrichi en hydrogène à l'unité de dessiccation.- Means for sending the hydrogen-enriched gas to the desiccation unit.

- des moyens pour envoyer un gaz enrichi en hydrogène de la colonne d'épuisement en aval de l'unité de decarbonatation.- Means for sending a gas enriched in hydrogen from the exhaust column downstream of the decarbonation unit.

L'unité de séparation cryogénique peut comprendre une colonne de lavage au méthane, une colonne d'épuisement et une colonne de rectification et des moyens pour soutirer le gaz enrichi en hydrogène de la colonne de lavage au méthane. D'autres types d'unité peuvent être envisagés, tels qu'une unité à condensation partielle.The cryogenic separation unit can comprise a methane washing column, a stripping column and a rectification column and means for withdrawing the hydrogen-enriched gas from the methane washing column. Other types of unit can be envisaged, such as a partial condensing unit.

Dans le cas de la présence d'un compresseur de gaz de synthèse, l'innovation proposée consiste à mettre en place une boucle de recycle d'un gaz riche en hydrogène entre la boîte froide et l'amont de l'unité de lavage aux aminés.In the case of the presence of a syngas compressor, the innovation proposed consists in installing a recycle loop of a hydrogen-rich gas between the cold box and the upstream of the washing unit at amines.

Ce gaz riche en hydrogène produit en sortie de la boîte froide par la colonne de lavage au méthane liquide, est utilisé comme gaz de régénération de l'épuration, est détendu et renvoyé à l'amont de l'unité de lavage aux aminés pour être mélangé au gaz de synthèse provenant de l'unité de génération. Aucun surplus d'hydrogène ne doit être produit.This hydrogen-rich gas produced at the outlet of the cold box by the liquid methane washing column, is used as a gas for regeneration of the purification, is expanded and returned upstream of the amine washing unit to be mixed with synthesis gas from the generation unit. No excess hydrogen should be produced.

Ceci a pour conséquence une diminution de la taille de l'unité de génération du gaz de synthèse de l'ordre de 5 à 15 %.This results in a reduction in the size of the synthesis gas generation unit of the order of 5 to 15%.

Un autre avantage est la récupération de la quantité de CO co-adsorbé dans l'unité de purification qui retourne dans la boucle de gaz de synthèse. Ceci a pour conséquence une augmentation du taux de récupération du monoxyde de carbone de l'ordre de 0,5 %.Another advantage is the recovery of the amount of CO co-adsorbed in the purification unit which returns to the synthesis gas loop. This results in an increase in the recovery rate of carbon monoxide of the order of 0.5%.

Le gaz de flash de la boîte froide peut être également recyclé à l'amont du compresseur de gaz de synthèse afin d'améliorer le rendement en CO de l'unité.The flash gas from the cold box can also be recycled upstream of the syngas compressor to improve the CO yield of the unit.

Tous les pourcentages mentionnés dans ce document sont des pourcentages molaires et les pressions sont des pressions absolues.All the percentages mentioned in this document are molar percentages and the pressures are absolute pressures.

L'invention sera maintenant décrite plus en détail en se référant aux dessins, dont la Figure 1 représente schématiquement la séparation du gaz de synthèse par plusieurs étapes dont la séparation cryogénique et la Figure 2 représente un appareil de séparation cryogénique adapté à être intégré dans laThe invention will now be described in more detail with reference to the drawings, in which Figure 1 schematically represents the separation of synthesis gas by several stages including cryogenic separation and Figure 2 represents a cryogenic separation device adapted to be integrated in the

Figure 1.Figure 1.

Dans la Figure 1 , un débit 1 de gaz de synthèse à environ 16 bars provenant d'un four de reformage à la vapeur d'eau F est séparé dans une unité 2 de lavage aux aminés afin d'enlever le dioxyde de carbone. Ce produit est ensuite comprimé dans un compresseur 3 jusqu'à une pression d'entre 18 et 43 bar abs. Le débit comprimé 4 est épuré en eau dans une unité d'épuration 5 pour produire un débit gazeux de 55500 Nm3/hr contenant 62 % d'hydrogène, moins d'un pour cent d'azote, 35 % de monoxyde de carbone et 3 % de méthane.In FIG. 1, a flow 1 of synthesis gas at approximately 16 bars originating from a steam reforming furnace F is separated in an amine washing unit 2 in order to remove the carbon dioxide. This product is then compressed in a compressor 3 to a pressure between 18 and 43 bar abs. The compressed flow 4 is purified with water in a purification unit 5 to produce a gas flow of 55,500 Nm 3 / hr containing 62% of hydrogen, less than one percent of nitrogen, 35% of carbon monoxide and 3% methane.

Ce débit est ensuite séparé dans un appareil de séparation cryogénique pour produire un produit gazeux 8 de 25400 Nm3/h constituant un mélange de monoxyde de carbone et d'hydrogène (typiquement 50 % d'hydrogène et un peu plus que 49 % de monoxyde de carbone), un produit gazeux 9 de 18700 Nm3/h riche en hydrogène (typiquement 99 % d'hydrogène), un produit gazeux 11 de 6500 Nm3/h riche en monoxyde de carbone (typiquement 99 % de monoxyde de carbone), une purge 13 de méthane, un gaz riche en hydrogène 7 et un gaz de flash 15 de 1300 Nm3/h (typiquement contenant 95 % d'hydrogène, 1 % de monoxyde de carbone et 4 % de méthane). Un débit de 1700 Nm3/h de gaz de paliers 14 contenant plus de 98 % d'hydrogène est envoyé à une turbine de détente.This flow is then separated in a cryogenic separation apparatus to produce a gaseous product 8 of 25,400 Nm 3 / h constituting a mixture of carbon monoxide and hydrogen (typically 50% of hydrogen and a little more than 49% of monoxide carbon), a gaseous product 9 of 18700 Nm 3 / h rich in hydrogen (typically 99% of hydrogen), a gaseous product 11 of 6500 Nm 3 / h rich in carbon monoxide (typically 99% of carbon monoxide) , a methane purge 13, a hydrogen-rich gas 7 and a flash 15 of 1300 Nm 3 / h (typically containing 95% hydrogen, 1% carbon monoxide and 4% methane). A flow of 1700 Nm 3 / h of bearing gas 14 containing more than 98% of hydrogen is sent to an expansion turbine.

Le débit 7 de 6800 Nm3/h est envoyé à l'unité d'épuration 5 dont il sert à régénérer un des lits d'adsorbants et ensuite, saturé en eau, il est mélangé avec le gaz de synthèse en amont de l'unité de lavage aux aminés 2.The flow 7 of 6800 Nm 3 / h is sent to the purification unit 5 of which it is used to regenerate one of the adsorbent beds and then, saturated with water, it is mixed with the synthesis gas upstream of the amino wash unit 2.

Optionnellement, une partie 17 du débit residuaire 15 peut être recyclé en amont du compresseur 3 et en amont ou en aval de l'unité de lavage aux aminés 2.Optionally, part 17 of the residual flow 15 can be recycled upstream of the compressor 3 and upstream or downstream of the amine washing unit 2.

L'hydrogène produit pur 9 est directement vendu comme produit pur sans purification par un PSA. Les débits de gaz de flash 15 et de purge méthane 13 sont trop faibles pour la régénération de l'épuration 5. La purge méthane 13 peut avantageusement être envoyée à l'entrée du four F.The pure product hydrogen 9 is directly sold as a pure product without purification by a PSA. The flash 15 and methane purge gas flow rates 13 are too low for the regeneration of the purification 5. The methane purge 13 can advantageously be sent to the inlet of the furnace F.

Ce recyclage de gaz riche en hydrogène 7 permet de diminuer la taille du four de reformage à la vapeur d'eau de près de 10 % et d'augmenter le rendement en CO de 0,5 %.This recycling of hydrogen-rich gas 7 makes it possible to reduce the size of the steam reforming furnace by almost 10% and to increase the CO yield by 0.5%.

En variante ou en addition, une partie 19 du gaz de synthèse GS peut être séparée en aval de l'unité de dessiccation 5 et renvoyée en amont de l'unité de decarbonatation 2. Ce débit 19 peut également servir à régénérer l'unité de dessiccation 5 avant d'être mélangé avec le gaz de synthèse non traité 1.As a variant or in addition, part 19 of the synthesis gas GS can be separated downstream from the drying unit 5 and returned upstream from the decarbonation unit 2. This flow 19 can also be used to regenerate the drying 5 before being mixed with untreated synthesis gas 1.

Ceci a comme avantage de permettre la réduction de la taille de la boîte froide de l'unité de séparation cryogénique 6.This has the advantage of allowing the reduction of the size of the cold box of the cryogenic separation unit 6.

La Figure 2 représente un appareil de séparation de gaz de synthèse 6 par distillation cryogénique. Les débits ayant les mêmes chiffres de référence que ceux de la Figure 1 correspondent aux débits désignés dans la Figure 1. L'appareil comprend une colonne de lavage au méthane K1 , une colonne d'épuisement K2 et une colonne de rectification K3. Le gaz de synthèse GS refroidi et épuré est envoyé en cuve de la colonne de lavage au méthane K1. Deux débits enrichis en hydrogène sont soutirés de la colonne, dont un débit 9 et un débit 7 soutiré quelques plateaux théoriques plus bas que le débit 9.Figure 2 shows a synthesis gas separation device 6 by cryogenic distillation. The flows having the same reference numbers as those in FIG. 1 correspond to the flows designated in FIG. 1. The apparatus comprises a methane washing column K1, a stripping column K2 and a rectification column K3. The cooled and purified synthesis gas GS is sent to the tank of the methane washing column K1. Two flows enriched in hydrogen are withdrawn from the column, including a flow 9 and a flow 7 withdrawn from a few theoretical plates lower than flow 9.

Le débit liquide 20 enrichi en méthane et monoxyde de carbone est séparé en un débit liquide 22 et un débit diphasique 23 et envoyé à la colonne K2. Le débit 23 est envoyé directement à la colonne K2 alors que le débit 22 est partiellement vaporisé (non-illustré) avant d'être envoyé à la colonne K2.The liquid flow 20 enriched in methane and carbon monoxide is separated into a liquid flow 22 and a two-phase flow 23 and sent to column K2. The flow 23 is sent directly to the column K2 while the flow 22 is partially vaporized (not shown) before being sent to the column K2.

En tête de la colonne d'épuisement K2, un gaz 15 enrichi en hydrogène est soutiré. En cuve de la colonne d'épuisement K2, un débit 24 contenant principalement du monoxyde de carbone et du méthane est soutiré, sous-refroidi (non-illustré) et séparé en deux débits 25 et 26. Le débit 25 est envoyé directement à la colonne K3, le débit 26 est vaporisé (non-illustré) et envoyé à la colonne K3. Le produit riche en monoxyde de carbone 11 est soutiré en tête de la colonne K3. En cuve de la colonne K3 est soutiré un débit de méthane liquide 27 qui est ensuite pressurisé dans une pompe P, divisé en deux et envoyé en partie en tête de la colonne d'épuisement K2 et pour le reste en tête de la colonne de lavage au méthane K1 , le débit 13 constituant le purge méthane.At the top of the stripping column K2, a gas 15 enriched in hydrogen is withdrawn. In the tank of the stripping column K2, a flow 24 containing mainly carbon monoxide and methane is withdrawn, sub-cooled (not shown) and separated into two flows 25 and 26. The flow 25 is sent directly to the column K3, the flow 26 is vaporized (not shown) and sent to column K3. The product rich in carbon monoxide 11 is withdrawn at the head of column K3. In the tank of the column K3 is withdrawn a flow of liquid methane 27 which is then pressurized in a pump P, divided in two and sent partly at the top of the stripping column K2 and for the rest at the top of the washing column with methane K1, the flow 13 constituting the methane purge.

Le rebouillage de cuve des colonnes K2 et K3 ainsi que la condensation en tête de colonne K3 est assuré par un cycle de monoxyde de carbone (non- illustré) de manière connue. Reboiling of the tanks of columns K2 and K3 as well as the condensation at the head of column K3 is ensured by a carbon monoxide cycle (not illustrated) in a known manner.

Claims

REVENDICATIONS 1. Procédé de production simultanée d'hydrogène et de monoxyde de carbone du type dans lequel on reçoit un gaz de synthèse, tel qu'un gaz de reformage d'hydrocarbures, contenant de l'hydrogène et du monoxyde de carbone provenant d'une unité de production de gaz de synthèse (F), on soumet le gaz de synthèse à une decarbonatation dans une unité de decarbonatation (2) et à une dessiccation dans une unité de dessiccation (5), puis à une séparation cryogénique dans une unité de séparation cryogénique (6) des constituants restants caractérisé en ce que l'on recycle un gaz contenant au moins 60 % d'hydrogène constitué par :1. Process for the simultaneous production of hydrogen and carbon monoxide of the type in which a synthesis gas is received, such as a hydrocarbon reforming gas, containing hydrogen and carbon monoxide from a synthesis gas production unit (F), the synthesis gas is subjected to decarbonation in a decarbonation unit (2) and to desiccation in a desiccation unit (5), then to a cryogenic separation in a cryogenic separation (6) of the remaining constituents, characterized in that a gas containing at least 60% hydrogen consisting of: i) un gaz (7) provenant de la séparation cryogénique et/oui) a gas (7) originating from the cryogenic separation and / or ii) une partie (19) du gaz de synthèseii) part (19) of the synthesis gas en amont de l'unité de decarbonatation et en aval de l'unité de production de gaz de synthèse.upstream of the decarbonation unit and downstream of the syngas production unit. 2. Procédé selon la revendication 1 dans lequel le gaz (7) contenant au moins 60% d'hydrogène est soutiré en tête d'une colonne de lavage au méthane (K1) de l'unité de séparation cryogénique (6), dans laquelle se séparent les constituants restants.2. Method according to claim 1 in which the gas (7) containing at least 60% of hydrogen is withdrawn at the head of a methane washing column (K1) of the cryogenic separation unit (6), in which the remaining constituents separate. 3. Procédé selon la revendication 1 dans lequel le gaz contenant au moins 60% d'hydrogène est une partie du gaz le plus pur en hydrogène produit (7).3. The method of claim 1 wherein the gas containing at least 60% hydrogen is part of the purest hydrogen gas produced (7). 4. Procédé selon la revendication 1 ou 2 dans lequel le gaz contenant au moins 60 % d'hydrogène (7) sert à régénérer l'unité de dessiccation (5) avant d'être envoyé en amont de l'unité de decarbonatation.4. Method according to claim 1 or 2 wherein the gas containing at least 60% hydrogen (7) is used to regenerate the drying unit (5) before being sent upstream of the decarbonation unit. 5. Procédé selon l'une des revendications précédentes dans lequel le gaz de synthèse épuré dans l'unité de decarbonatation (2) est comprimé dans un compresseur (3) avant d'être envoyé à l'unité de dessiccation (5). 5. Method according to one of the preceding claims in which the synthesis gas purified in the decarbonation unit (2) is compressed in a compressor (3) before being sent to the desiccation unit (5). 6. Procédé selon la revendication 5 dans lequel un autre gaz enrichi en hydrogène (17) est envoyé de la séparation cryogénique en amont du compresseur et en aval de l'unité de decarbonatation.6. The method of claim 5 wherein another gas enriched in hydrogen (17) is sent from the cryogenic separation upstream of the compressor and downstream of the decarbonation unit. 7. Installation de production simultanée d'hydrogène et de monoxyde de carbone comprenant des moyens pour recevoir un gaz de synthèse provenant d'une unité de production de gaz de synthèse (F), une unité de decarbonatation (1), une unité de dessiccation (5) et une unité de séparation cryogénique (6), et des moyens reliant l'unité de production de gaz de synthèse avec l'unité de decarbonatation, l'unité de decarbonatation avec l'unité de dessiccation et l'unité de dessiccation avec l'unité de séparation cryogénique et des moyens de soutirage d'hydrogène et de monoxyde de carbone en tant que produits caractérisée en ce qu'elle comprend des moyens pour recycler un gaz contenant au moins 60 % d'hydrogène constitué par :7. Installation for the simultaneous production of hydrogen and carbon monoxide comprising means for receiving a synthesis gas originating from a synthesis gas production unit (F), a decarbonation unit (1), a desiccation unit (5) and a cryogenic separation unit (6), and means connecting the synthesis gas production unit with the decarbonation unit, the decarbonation unit with the desiccation unit and the desiccation unit with the cryogenic separation unit and means for drawing off hydrogen and carbon monoxide as products, characterized in that it comprises means for recycling a gas containing at least 60% hydrogen consisting of: i) un gaz enrichi en hydrogène, par rapport au gaz de synthèse, provenant de l'unité de séparation cryogénique et/oui) a gas enriched in hydrogen, relative to the synthesis gas, coming from the cryogenic separation unit and / or ii) une partie (19) du gaz de synthèseii) part (19) of the synthesis gas en amont de l'unité de decarbonatation (2) et en aval de l'unité de production de gaz de synthèse (F).upstream of the decarbonation unit (2) and downstream of the synthesis gas production unit (F). 8. Installation selon la revendication 7 comprenant des moyens de compression (3) en aval des moyens de decarbonatation (2).8. Installation according to claim 7 comprising compression means (3) downstream of the decarbonation means (2). 9. Installation selon la revendication 7 ou 8 comprenant des moyens pour envoyer le gaz enrichi en hydrogène à l'unité de dessiccation (5).9. Installation according to claim 7 or 8 comprising means for sending the gas enriched in hydrogen to the desiccation unit (5). 10. Installation selon la revendication 7, 8 ou 9 dans laquelle l'unité de séparation cryogénique (6) comprend une colonne de lavage au méthane (K1), une colonne d'épuisement (K2), une colonne de rectification (K3) et des moyens pour soutirer le gaz enrichi en hydrogène de la colonne de lavage au méthane.10. Installation according to claim 7, 8 or 9 in which the cryogenic separation unit (6) comprises a methane washing column (K1), a stripping column (K2), a rectification column (K3) and means for withdrawing the hydrogen-enriched gas from the methane washing column. 11. Installation selon la revendication 10 comprenant des moyens pour envoyer un gaz (17) enrichi en hydrogène de la colonne d'épuisement (K2) en aval de l'unité de decarbonatation (2). 11. Installation according to claim 10 comprising means for sending a gas (17) enriched in hydrogen from the exhaustion column (K2) downstream of the decarbonation unit (2).
PCT/FR2003/001174 2002-04-15 2003-04-14 Method and installation for separating a mixture of hydrogen and carbon monoxide Ceased WO2003086965A1 (en)

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JP4440653B2 (en) 2010-03-24
JP2005522396A (en) 2005-07-28

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